Slavko Mentus

Conducting carbonized polyaniline nanotubes

Conducting nitrogen-containing carbon nanotubes were synthesized by the carbonization of self-assembled polyaniline nanotubes protonated with sulfuric acid. Carbonization was carried out in a nitrogen atmosphere at a heating rate of 10 degrees C min(-1) up to a maximum temperature of 800 degrees C. The carbonized polyaniline nanotubes which have a typical outer diameter of 100-260 nm, with an inner diameter of 20-170 nm and a length extending from 0.5 to 0.8 microm, accompanied with very thin nanotubes with outer diameters of 8-14 nm, inner diameters 3.0-4.5 nm and length extending from 0.3 to 1.0 microm, were observed by scanning and transmission electron microscopies. Elemental analysis showed 9 wt% of nitrogen in the carbonized product. Conductivity of the nanotubular PANI precursor, amounting to 0.04 S cm(-1), increased to 0.7 S cm(-1) upon carbonization. Molecular structure of carbonized polyaniline nanotubes has been analyzed by FTIR and Raman spectroscopies, and their paramagnetic characteristics were compared with the starting PANI nanotubes by EPR spectroscopy.

Carbonised polyaniline and polypyrrole: towards advanced nitrogen-containing carbon materials

Polyaniline (PANI) and polypyrrole (PPY) undergo carbonisation in an inert/reduction atmosphere and vacuum, yielding different nitrogen-containing carbon materials. This contribution reviews various procedures for the carbonisation of PANI and PPY precursors, and the characteristics of obtained carbonised PANI (C-PANI) and carbonised PPY (C-PPY). Special attention is paid to the role of synthetic procedures in tailoring the formation of C-PANI and C-PPY nanostructures and nanocomposites. The review considers the importance of scanning and transmission electron microscopies, XPS, FTIR, Raman, NMR, and EPR spectroscopies, electrical conductivity and adsorption/desorption measurements, XRD, and elemental analyses in the characterisation of C-PANIs and C-PPYs. The application of C-PANI and C-PPY in various fields of modern technology is also reviewed.

Synthesis and characterization of self-assembled polyaniline nanotubes/silica nanocomposites.

Self-assembled semiconducting, paramagnetic polyaniline nanotubes have been synthesized by the oxidative polymerization of aniline with ammonium peroxydisulfate in aqueous medium in the presence of colloidal silica particles of an average diameter approximately 12 nm, without added acid. The electrical conductivity of polyaniline nanotubes/silica nanocomposites is in the range (3.3-4.0)x10(-3) S cm(-1). The presence of paramagnetic polaronic emeraldine salt form of polyaniline and phenazine units in nanocomposites was proved by FTIR, Raman, and EPR spectroscopies. The influence of the initial silica/aniline weight ratio on the morphology of polyaniline/silica nanocomposites was studied by scanning and transmission electron microscopies. Nanocomposites synthesized by using the initial weight ratio silica/aniline<or=0.2 contain polyaniline nanotubes which have a typical outer diameter of 100-250 nm and an inner diameter of 10-80 nm, and nanorods with a diameter of 60-100 nm, accompanied with polyaniline/silica nanogranules, while the nanocomposite synthesized at weight ratio silica/aniline approximately 2 contains polyaniline/silica nanogranules with an average diameter of 35-70 nm. The evolution of molecular and supramolecular structure of polyaniline in the presence of colloidal silica is discussed.

Synthesis and Characterization of Conducting Self-Assembled Polyaniline Nanotubes/Zeolite Nanocomposite

Self-assembled conducting, paramagnetic polyaniline nanotubes have been synthesized by the oxidative polymerization of aniline with ammonium peroxydisulfate in aqueous medium in the presence of zeolite HZSM-5, without added acid. The influence of initial zeolite/aniline weight ratio on the conductivity, molecular and supramolecular structure, paramagnetic characteristics, thermal stability, and specific surface area of polyaniline/zeolite composites was studied. The conducting (approximately 10(-2) S cm(-1)), semiconducting (3 x 10(-5) S cm(-1)), and nonconducting (5 x 10(-9) S cm(-1)) composites are produced using the zeolite/aniline weight ratios 1, 5, and 10, respectively. The coexistence of polyaniline nanotubes, which have a typical outer diameter of 70-170 nm and an inner diameter of 5-50 nm, accompanied by nanorods with a diameter of 60-100 nm and polyaniline/zeolite mesoporous aggregates, distinct from the morphology of microporous zeolite HZSM-5, was proved in the conducting nanocomposite by scanning and transmission electron microscopies. FTIR spectroscopy confirmed the presence of polyaniline in the form of conducting emeraldine salt and suggested significant interaction of polyaniline with zeolite. The evolution of molecular and supramolecular structure of polyaniline in the presence of zeolite was discussed.

Hydrogen Adsorption on Palladium and Platinum Overlayers: DFT Study

Hydrogen adsorption on twenty different palladium and platinum overlayer surfaces with (111) crystallographic orientation was studied by means of periodic DFT calculations on the GGA-PBE level. Palladium and platinum overlayers here denote either the Pd and Pt mono- and bilayers deposited over (111) crystallographic plane of Pd, Pt, Cu, and Au monocrystals or the (111) crystallographic plane of Pd and Pt monocrystals with inserted one-atom-thick surface underlayer of Pd, Pt, Cu, and Au. The attention was focused on the bond lengths, hydrogen adsorption energetics, mobility of adsorbed hydrogen, and surface reactivity toward hydrogen electrode reactions. Both the ligand and strain effects were considered, found to lead to a significant modification of the electronic structure of Pd and Pt overlayers, described through the position of the d-band center, and tuning of the hydrogen adsorption energy in the range that covers approximately 120 kJmol−1. Mobility of hydrogen adsorbed on studied overlayers was found to be determined by hydrogen-metal binding energy. Obtained results regarding Pd layers on Pt(111) and Au(111) surfaces, in conjunction with some of the recent experimental data, were used to explain its electrocatalytic activity towards hydrogen evolution reaction.

Bromide oxidation and bromine reduction in propylene carbonate

Abstract Bromide oxidation and bromine reduction in propylene carbonate (PC) +1 M LiClO 4 was investigated voltammetrically using polycrystalline platinum rotating disc electrode. The corresponding voltammograms were compared to those of iodide oxidation and HCl decomposition. The oxidation 2Br − →Br 2 +2e − was found to proceed through two steps, which are caused by the formation of a stable intermediate Br 3 − ion. The stability constant of tri-bromine ion was estimated to be 10 5.5 M. The diffusion coefficient of Br − ion in this solution was determined to be 3.41×10 −6 cm 2 s −1 . In the case of bromine reduction, a time dependence of the shape of the voltammogram was observed, which showed that one is dealing with a direct bromination of PC.

Systematic DFT-GGA study of hydrogen adsorption on transition metals

Computational study of hydrogen adsorption on (111) surface of transition metals with face centered cubic (fcc) lattice is reported and the results are compared with available experimental and theoretical data. In addition, dissociative adsorption of hydrogen on Pt(111), Pt(100) and Pt(110) is studied in the range of coverage from 0.25 to 1 monolayer. In the case of Pt(111) preferential adsorption site was found to be three-coordinated fcc-hollow site, while on Pt(100) and Pt(110) surface hydrogen settles on two-coordinated bridge and short bridge site, respectively. Hydrogen adsorption energy was found to decrease with the increasing coverage. Structural changes of studied Pt surfaces upon hydrogen adsorption have been compared with the experimental data existing in the literature and good qualitative agreement has been obtained.

Thin layer of Ni-modified 13X zeolite on glassy carbon support as an electrode material in aqueous solutions

A new type of an electrode material, zeolite modified by the incorporation of Ni or NiO clusters into its cavities, was synthesized by multiple impregnation of zeolite 13X with a Ni-acetylacetonate solution followed by solvent evaporation and thermal degradation of the nickel compound. Samples with a Ni/13X mass ratio within the range 0.2–1.0 were synthesized. Modification by both Ni and NiO clusters, depending on whether the atmosphere was reducing (H2) or oxidizing (air), respectively, was used to finish the sample. After modification, the zeolite kept its original crystallographic structure, as proven by X-ray diffractommetry. The dimensions of the incorporated clusters were limited by the diameter of the zeolite cavities (reaching 1.3 nm). This material, homogenized with 10 wt % of nanodispersed carbon, was bonded in the form of a thin layer to a glassy carbon disc by means of Nafion and used as an electrode material in an aqueous 0.1 M NaOH solution. The cyclovoltammograms of this thin-layer electrode resemble those of a smooth nickel electrode in alkaline solutions.

Introduction of Pt and Pd Nanoclusters in Zeolite Cavities by Thermal Degradation of Acetylacetonates

Nanodispersed metallic clusters of platinum and palladium were incorporated into NaX zeolite cavities by impregnation with acetone solution of corresponding acetylacetonates, solvent evaporation and acetylacetonate thermal decomposition. The acetylacetonate decomposition was followed by thermogravimetry. Modified zeolite samples were characterized by x-ray diffractommetry. In order to get a satisfactory electronic conductivity of modified zeolite, 10 % wt of carbon black was added. This material was applied to a rotating glassy carbon disc electrode, and was used to study electrochemical water splitting in slightly acidic aqueous solutions. Noble metal modified zeolites exhibit significant reduction in water decomposition overvoltage as compared to smooth polycrystalline platinum.

Conductivity, viscosity and IR spectra of Li, Na and Mg perchlorate solutions in propylene carbonate/water mixed solvents

The influence of water addition on the electric conductivity, viscosity and IR spectra of Mg, Li and Na perchlorate solutions in propylene carbonate (PC) was examined. Conductivity and viscosity data pointed out ion–solvent and ion–ion associations that were most pronounced in Mg(ClO4)2 solutions. IR investigations were directed towards the spectral region 1000–600 cm-1. The changes of the ν4 band of the perchlorate anion at 624 cm-1 and the changes of solvent bands in the spectral region 980–890 cm-1 caused by water addition to 1 M solutions indicated the formation of contact ion pairs. The appearance and increase in intensity of the otherwise IR-inactive perchlorate band at 931 cm-1, upon water addition, was attributed to cation–H2O–ClO4- solvent shared ion pairs.